Mercapto aryl thiazoles and method of making them



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Patented Apr. 25, 1933 I UNITED sT SIDNEY M. CADWELL, on LEONTA, New mess ASSIGNOB: To run NAUGATUGK CHEMICAL COMPANY, or NAUGATUGK, connnorroucr, A oonronerron or; con- I nncrrcur 2 MERCAPTO ARYL 'rHIAZoLEs AND METHOD or MAKING THEM" No Drawing. Application filed March 2,

This invention-relates toa new class of chemical productsiand to methods of making them. I

The invention consists in treating a solution of a'thiol acid with asolutionof a halide of. an organic group to produce new compounds containing the group Rosy.

, ll 7 X 4 o The invention includes the newproducts thus obtained In V V aosY.

R represents sulphurX represents a trivalent element as in the case of a thiazole Y is a substituted aryl or methyl group having a carbon atom thereof directly attached to the sulphur of the original sulfhydryl group. The mercapto thiazoles afford an example in which the R and X are parts of a ring.

As illustrations of Y the following are given :-2-4 dinitrophenyl, 2-6. dinitro 4 chloro phenyl, 2-4-6 trinitro phenyl (picryl) etc., diphenyl methyl, triphenyl methyl, phenyl methylene (benzal) trimethyl methyl (tertiary butyl), phenyl chlor methylene, phthalimidomethyl, diiodomethyl, allyl etc. In the examples of poly nitro phenyl groups it will be observed that there is at least :one nitro group ortho to the 1-position, and that at least one of the remaining substituents is meta to the aforesaid nitro group. In the 'dinitro phenyl groups, the two nitro groups 140 grams of sodium hydroxide are dis- 1928. "serial mutate;

solved in 500 grams ofiwater and 168 grams of mercaptobenzothiazole and 500 cc. of

95% alcohol are added. The mixture is cipitates out is removed by filtration,

washed free of sodium chloride, dried and ground. The melting point should be 156 157? C. On further purification the .melting point is 162 Itiis 'a yellow material crystallizing inprismsjjthat meltat 162 C. uncorrected. Thefbody is insoluble in water and practically insoluble in cold alcohol. It isfairly soluble in hot alcohol, quite soluble in warm benzol and fairly soluble even in cold benzol. It is soluble in cold acetone. Itsalcoholicssolution hydrolyzes in the: presence of alkali. The. probable formula is V C S:-CH3(N0fl 2- I Another example of this class of compounds is 2, 4, 6 trinitrophenyl benzothiazyl sulphide. It may be prepared as follows:

168 grams of mer'capto b'enzothiazole are dissolved in 500 cc. of alcohol and 500 cc.

of waterv by means of 40, grams of. sodium 5 hydroxide.

The solution then contains the sodium salt of mercapto benzothiazole. To

this solution are added 247 grams of 1 trinitrophenyl 'benz'othiazyl sulphide crystallizes 01111.1" This is filtered from the reaction liquor, washedv free from-sodium chloride, and dried. It is a brick-red crystalline -materialmelting after re-crystallization from alcohol at 152, C. uncorrected. It is a Another example of this class of compounds is 2, 6 dinitro 4 chlo'rophenyl benzothiazyl sulphide which may be prepared as follows: l

168 grams of mercapto benzothiazole are dissolved in 500' cc. of alcohol and 500 cc. of water by means of the addition of 40 grams of sodium hydroxide. The solution then contains the sodium salt of mercapto benzothiazole. To this solution are added 237 grams of 2, 6 dinitro 1, 4 dichlorobenzol and the whole heated to 60-70 until all of the 2, 6 dinitro 1, 4 'dichlorobenzol has disappeared. The reaction mixture is then cooled toroom temperature whereupon the product which is the 2, 6 dinitro 4 chlorophenyl ben- Zothiazylsulphide crystallizes out. This is filtered from the reaction mixture, washed free of sodium chloride'and dried.- This is a yellow body, soluble in benzol, quite soluble in hot alcohol andfairly soluble in cold alcohol. The melting point is 167 C. uncorrected. The formula is The allyl, diphenyl methyl, phenyl methylene-and other derivatives of mercapto benzo thiazole may be similarly prepared. In all of this class of compoundsR and X in the group RpsY are sulphur and nitrogen respectively, and the group may be written sosY.

These compounds contain the group I Other benzo thiazyl sulphides include: Allyl benzo thiazyl sulphide-B. P. 145148 (3., diphenylmethylbenzothiazyl sulphideM. P. 108 (3., phenyl methylene bis benzo thiazyl sulphide (M. P. 114 (3.).

The new compounds are in general soluble in benzol, acetone and hot alcohol, slightly soluble in cold alcohol, and insoluble in water. All of the compounds described herein are of utility in the vulcanization of rubber.

Having thus described my invention, what I claim and desire to protect by Letters Patcut is:

1. A method of making picryl benzo .thiazyl sulphide which comprisestreating an alcoholic solution of mercapto benzo thiazole and aqueous sodium hydroxide with chloro 2-4-6 trinitro benzene, heating until the reaction is complete, cooling, separating out the reaction product, and purifying it. 7 v

2. A process of preparing athiazole derivative whichcomprises reacting an alkali salt of mercapto benzothiazol'e and a nitrochlorbenzene.

3. A process of. preparing a thiazole de rivative which comprises-reacting an alkali saltof mercapto benzothiazole and dinitrochlorbenzene.

4. A process of preparing a thiazole .derivative which comprises reacting .an alkali metal salt of mercapto benzothiazole anda nitrochlorbenzene. u

5. A process of preparing a thiazole derivative which comprises reacting the sodium salt of mercapto-benzothiazole and a nitrochlorbenzene. i

6. As a new compound a benzothiazyl sulfid containing a di-substituted phenyl group attached to said sulfid grouping, at least one of said substituents comprising a nitro group. y

7. As a new compound a benzo thiazole derivative containing the group where 'Y represents a disubstituted aryl I group containing a nitro substituent, said aryl group Y containing less than eight carbon atoms. i 8. As a new compound, a derivative of mercapto benzo thiazole wherein a nitro substituted aryl group is attached to a sulphur atomof the thiazole, said aryl group containing less than eight carbon atoms and including only carbon, hydrogen, nitrogen andoxygen within its structure. I "9. As a new compound, a derivative of mercapto benzo thiazole wherein a disubstituted benzene, one of which substituents is a nitro group, is attached to a sulfur atom of the thiazole, said substituted benzene containing less than eight carbon atoms and including only carbon, hydrogen, nitrogen and oxygen within its structure.

10. A method of making a nitro substituted aryl-benzo-thiazyl sulfid which comprises treating mercapto benzothiazole with a nitro substituted aryl halide, containing less than eight carbon atoms, separating the reaction product and purifying. r

11. A method of making a nitro substituted aryl benzothiazyl sulfid which comprises re acting in the presence of an organic solvent mercapto benzothiazole, and alkali and a nitro substituted aryl halide containing less than eight carbon atoms, separating the recompound-containing less than eight carbon atoms and separating the reaction product.

13. A method of forming a benzo thiazyl sulfid containing a substituted phenyl group attached to said sulfid grouping, which comprises reacting in the solvent, a mercaptobenzothiazole, an alkali and a cli-substituted benzene containing less than eight carbon atoms, the latter containing a nitro group, and separating the reaction product.

14:. As new compounds, mercapto aryl thiazoles of the formula where R is an arylene group and Y is an aryl or methyl group which is substituted by at least one substituent having a negative character.

15. As new materials, mercapto aryl. thiazoles wherein the sulphur of the original sulfhydryl group is directly attached, through substitution of the hydrogen of said last group,to a carbon atom in a substituted group comprising at least one single benzene nucleus, said last mentioned group comprising more than carbon and hydrogen.

16. As new materials, mercapto aryl thi azoles wherein the sulphur of the original sulfhydryl group is directly attached, through replacement of the hydrogen of said last group, to a carbon atom in a substituted aromatic group of the benzene series, said last mentioned group comprising more than carbon and hydrogen. 7

17 .As new materials, mercapto aryl thiazoles wherein the sulphur of the original sulfhydryl group is directly attached, by replacement of the hydrogen of said last group, to a carbon atom in a substituted phenyl group, said last mentioned group comprising more than carbon and hydrogen.

18. As a new compound, an arylene thiazyl sulphide containing the group where Y is a methyl group which is substituted by at least one substituent having a negative character.

19. As a new compound phenyl methylene presence of an organic bis benzo thiazyl sulphide having the probable general formula 20. As a new compound a benzothiazyl sulphide containing the group whereY consists of a phenyl group and at least one acidic substituent.

21. As a new compound a benzothiazyl sulphide containing the group where Y .respresents a polynitrophenyl group.

22. As a new compound a benzothiazyl sulphide containing the group Signed at New York, county and New State a York, this 23rd day of February, 1928.

. SIDNEY M. GADWELL. 

